Method for suppressing the nitrification of ammonium nitrogen present in soil



Law

METHQD FOR SUPPRESSENG THE NITRIFICA- TION F AMIVIONIUM NITROGEN PRESENT 1N SOIL Cleve A. I. Goring, Garden Grove, Calif, assignor to The Dow Chemical Company, Midland, Mich., a corporation of Delaware No Drawing. Filed Apr. 11, 1957, Ser. No. 652,315

12 Claims. (Cl. 711) The present invention relates to crop culture and is particularly concerned with a new agronomical practice and composition for conserving soil nitrogen and for supplying the soil nitrogen requirements for plant nutrition.

Since the majority of plants obtain most or all of their nitrogen requirements from the soil, the adequate provision of nutrient nitrogen in soil for plant growth is one of the foremost agronomic problems. The nitrogen in the soil is found to occur primarily in three forms: organic nitrogen, ammonium nitrogen and nitrate nitrogen, of which ammonium nitrogen and nitrate nitrogen are the primary forms utilized by plants. This nitrogen is absorbed by plants in solution from the soil in the form of ammonium ions and nitrate ions.

The organic nitrogen in the soil consists of a large number of compounds and originates from manure, crop residues, organic fertilizers or bacterial syntheses. Since with the exception of the organic reduced nitrogen fertilizers such as urea, the solubility .of these compounds in water is very low, they are not readily leached from the soil, but neither are they directly available to the plants for use. In order to be available to the plants, the nitrogen in the organic compounds must be converted by soil bacteria to ammonia or inorganic ammonium salts. This conversion, when from organic reduced nitrogen fertilizers such as urea, takes place very rapidly, but very slowly when from other organic nitrogen compounds. Following the conversion, the ammonium nitrogen is very rapidly oxidized by soil bacteria to inorganic nitrate nitrogen. In this process, the ammonium nitrogen is first oxidized to the intermediate nitrite nitrogen which is then rapidly oxidized to nitrate nitrogen. This mineralization of organic nitrogen constantly replenishes the soil with nitrogen available for plant absorption.

The ammonium nitrogen in the soil is derived from bacterial conversion of organic nitrogen or from the added reduced nitrogen fertilizers such as anhydrous ammonia, aqueous ammonia, ammonium phosphate, ammonium nitrate and ammonium sulfate. These ammonium compounds or inorganic reduced nitrogen compounds are readily soluble in water or aqueous soil medium. When in solution, the reduced nitrogen occurs largely as the ammonium ion. Due to the cationic nature of this ion, the ion is strongly adsorbed on the soil colloids or base exchange complex of the soil. This colloidal-bound ammonium nitrogen exists in equilibrium with a small concentration of ammonium ions in the soil solution. Thus, the colloidal-bound ammonium nitrogen provides a dynamic nitrogen reservoir to maintain a supply of ammonium ions in the soil solution for plant adsorption. Further, since the ammonium nitrogen in the soil occurs principally as colloidal-bound nitrogen, only very small quantities of the ammonium form of soil nitrogen are lost from the feeding zone of the plants by leaching.

The nitrate nitrogen in the soil is derived from the oxidation or nitrification of ammonium nitrogen by soil bacteria, or by the addition of inorganic nitrate fertilizers such as ammonium nitrate, sodium nitrate, potassium nitrate and calcium nitrate. The inorganic nitrate compounds are readily soluble in Water and the aqueous soil medium. When so dissolved, the nitrate nitrogen largely exists as the nitrate ion. Because of the anionic nature of this ion, nitrate nitrogen is not adsorbed by soil colloids. Accordingly, the nitrate nitrogen is rapidly leached by rainfall and irrigation and readily lost from the feeding zone of the plants. Further, the nitrate nitrogen is reduced by many soil bacteria to nitrogen gas. The latter process is known as denitrification and accounts for an additional loss of large quantities of nitrate nitrogen from the soil. The yearly loss from leaching and denitrification amounts to from 20 to percent of the nitrate nitrogen found in the soil, whatever its source.

Nitrification or the conversion of the ammonium nitrogen in soil to nitrate nitrogen by bacterial action occurs at a rate which is dependent primarily upon the soil temperature and the soil pH. The rate is also somewhat dependent upon the type of soil and the moisture content of the soil. The rate of nitrification is rapid when the soil temperature is at least 10 C. and the soil pH is at least 5. For example, the conversion of ammonium nitrogen to nitrate nitrogen in sand, silt or clay loam soil having a pH of at least 6 may take place at a rate of from 20 pounds of nitrate nitrogen per acre per week at 10 C., to 500 pounds of nitrate nitrogen per acre per week at 35 C. Even at temperatures as low as 2 C., nitrification will oftentimes occur in such soils at a rate of 25 pounds of nitrate nitrogen per month. Thus, ammonium nitrogen is very rapidly changed to nitrate nitrogen in most agricultural soils.

The tremendous losses of soil nitrogen resulting from the rapid nitrification of ammonium nitrogen, and the leaching and bacterial decomposition of nitrate nitrogen have depleted many agricultural soils of the nitrogen re serves and nitrogen requirements for plant nutrition. In order to replenish the soil nitrogen, the agriculturalist has resorted to the use of large amounts of nitrate fertilizers and reduced nitrogen fertilizers. In many instances, multiple fertilizer treatments during the growing season have been required to maintain adequate nitrogen requirements for plant growth. In this practice, the greater proportion of the employed fertilizers is in the form of reduced nitrogen fertilizers. By the expression reduced nitrogen fertilizers is meant fertilizers containing nitrogen in the reduced state including ammonium salts, ammonia, and Water-soluble organic compounds readily convertible in the soil to ammonia or ammonium ions such as urea and cyanamide.

Since the nitrogen must be present as nitrate nitrogen before substantial quantities can be leached from the soil or lost by denitrification, the application of nitrogen as reduced nitrogen fertilizers provides the agriculturalist with a short interval during which available reduced nitrogen is at a maximum and conditions for leaching and denitrification are at a minimum. This interval is particularly advantageous during the initial growth of seeds and emerging seedlings when high soil nitrogen concentrations are very desirable. In addition, the ammonium nitrogen absorbed by plants is immediately available for assimilation into organic materials being synthesized thereby. In contrast, the nitrate nitrogen must be reduced before it can be assimilated in the synthesis of plant materials. This reduction is carried out in the plant usually at the expense of synthesized carbohydrate. Although some plants seem to do Well on either ammonium nitrogen or nitrate nitrogen as a source of nitrogen nutrients, many plants such as potato, corn, rice,

Patented Nov. 21, 1961 3 buckwheat, pineapple, cotton and orange prefer ammonium nitrogen and appear to grow best on this form of nitrogen. Thus, the need for a method of suppressing the rapid loss of soil nitrogen is well recognized by the agriculturalists.

An object of the present invention is to provide a new and improved agronomic practice for conserving soil nitrogen. A further object is the provision of a new and improved method for suppressing the loss of soil nitrogen. An additional object is the provision of a new and improved method for suppressing the loss of ammonium nitrogen from soil. Another object is the provision of a new and improved method for supplying soil with nitrogen available for plant growth. Another object is the provision of a new and improved method for suppressing the loss of reduced nitrogen fertilizer supplements from soil. An additional object is the provision of a new and improved method for suppressing the nitrification of ammonium nitrogen in soil. Another object is the provision of a new and improved method for suppressingthe conversion in soil of ammonium ions to nitrate ions. An additional object is the provision of novel compositions to be employed in the new methods of the present invention. Other objects will become apparent from the following specification and claims.

The new agronomical practice for improving plant nutrition and conserving soil nitrogen comprises treating plant growth media with a phenol compound comprising (1) phenols having the formula wherein X represents hydrogen, bromine, chlorine or methyl, Y represents nitro or hydrogen and Z represents methyl or hydrogen; and wherein the phenolic ring is substituted by at least one of (a) a nitro radical and (b) both a methyl and a halo radical; and wherein the phenolic ring contains no more than one methyl radical; and (2) salts of said phenols. Examples of such phenols include 4-chloro-2-methyl-6-nitrophenol, 4-chloro-2-nitrophenol, 2-nitrophenol, 4-chloro-2-methylphenol, 4- bromo-2-methylphenol, 4-bromo-2-methyl-6-nitrophenol, 4-bromo-2-nitrophenol, 2-nitro-4-methylphenol, and 2- methyl-G-nitrophenol. Suitable salts include alkali and alkaline earth metal salts such as sodium, potassium, calcium; ammonium and quaternary ammonium salts such as tetramethylammonium, trimethylethylammonium and dimethyldiethylammonium; monoand polyalkylamines such as methylamine, diisopropylamine and dimethyldodecylamine; cyclic amine-s such as piperidine; monoand polyalkanolamine salts such as triethanolamine and isopropanolamine; and alkylene polyamine salts such as propylenediamiue, ethylenediamine, etc. The phenol compounds are crystalline solid materials which are adapted to be readily and conveniently distributed in soil. By the practice of this invention, the nitrification of ammonium nitrogen in the soil to nitrate nitrogen is suppressed thereby preventing the rapid loss of ammonium nitrogen from the soil. Furthermore, by proper distribution, this action of inhibiting the transformation of ammonium nitrogen to nitrate nitrogen is effective over a prolonged period of time. The ammonium nitrogen may arise from added ammonium nitrogen fertilizers or be formed in the soil by conversion of the organic nitrogen constituents found in soil or added thereto as components of organic fertilizers.

The provision of an efiective dosage of the phenol compounds in the soil or growth medium is essential for the practice of the present invention. In general, good results are obtained when the growth medium is supplied with the compounds in the amount of from 2 to 150 parts or more by weight per million parts by weight of growth medium. In field applications, the compounds may be distributed in the soil in the amount of at least 0.5 pound per acre and through such a cross-section of the soil as to provide for the presence therein of an effective concentration of the agent. It is usually preferred that the compounds be distributed to a depth of at least two inches below the soil surface and at a dosage of at least 0.7 pound per acre inch of soil. By dispersing very large dosages in growth media, a prolonged inhibition of nitrification may be obtained over a period of many months. The concentration of the active compounds is eventually reduced to a minimum by decomposition in the soil.

In one embodiment of the present invention, the active compounds are distributed throughout the growth media prior to seeding or transplanting the desired crop plant.

In another embodiment, the soil in the root zone of growing plants is treated with the active compounds in an amount to inhibit nitrification but sublethal to plant growth. In such operations, the compounds should be supplied in the soil in an amount no greater than about 50 parts by weight per million parts by weight of the soil. By following such practice, no adverse effect is exerted by the compounds upon growth of seeds or plants. Oftentimes it is desirable to treat the soil adjacent to plants, and this procedure may be carried out conveniently in side-dressing operations.

In a further embodiment, soil may be treated with the compounds following harvest or after fallowin g to prevent rapid loss of ammonium nitrogen and to build up the ammonium nitrogen formed by conversion of organic nitrogen compounds. Such practice conserves the soil nitrogen for the following growing season.

In an additional embodiment, the soil is treated with phenolic compounds in conjunction with the application of reduced nitrogen fertilizers. The treatment with the phenolic compounds may be carried out prior to, subsequent to or simultaneously with the application of fertilizers. Such practice prevents the rapid loss of the ammonium nitrogen added as fertilizer and the ammonium nitrogen formed from the organic reduced nitrogen in fertilizers by the action of soil bacteria. The administration to the soil of the phenolic compounds in an ammonium nitrogen fertilizer composition constitutes a preferred embodiment of the present invention.

The present invention may be carried out by distributing the phenol compounds in an unmodified form through growth medium. The present method also embraces distributing the compound as a constituent in liquid or finely divided solid compositions. In such practice, the phenolic compounds may be modified with one or more additaments or soil treating adjuvants including water, petroleum distillates or other liquid carriers, surface-active dispersing agents, finely divided inert solids and nitrogen fertilizers. Depending upon the concentration of the compounds, such augmented compositions may be distributed in the soil without further modification or be considered concentrates and subsequently diluted with additional inert carrier to produce the ultimate treating compositions. The required amount of the compounds may be supplied to growth media in from 1 to 50 gallons of organic solvent carrier, in from 5 to 27,000 or more gallons of aqueous carrier, or in from about 20 to 2,000 pounds of solid carrier per acre treated.

The concentration of the compounds in compositions to be employed for the treatment of growth media is not critical and may vary considerably provided the required dosage of eifective agent is supplied thereto. The concentration of the phenol compound may vary from 0.001 percent by weight to percent by weight of the composition, depending on whether the composition is a treating composition or a concentrate composition and whether it is in the form of a solid or a liquid. In aqueous liquid treating compositions, concentrations of from 0.001 percent to 0.25 percent by weight of the phenolic compound is considered the preferred composition. The

concentration of the phenolic compound in organic solvents may be from 2.0 to 50 percent by weight. Concentrate liquid compositions generally contain from 2.5 to 50 percent by weight of the phenol compound. Solid compositions may contain the phenolic compound in amounts as high as 95 percent by weight of the active compound. Treating compositions generally contain 0.004 percent to percent by weight of the phenol compound. Solid concentrate compositions contain from 2.5 to 95 percent of the phenolic compound.

Liquid compositions containing the desired amount of the compounds may be prepared by dispersing the agents in one or more liquid carriers such as water and organic solvents with or without the aid of a suitable surfaceactive dispersing agent or emulsifying agent. Suitable organic solvents include acetone, diisobutylketone, methanol, ethanol, isopropyl alcohol, diethyl ether, toluene, methylene chloride, chlorobenzene and the petroleum distillates. The preferred organic solvents are those which are of such volatility that they leave little permanent residue in the soil. When the solutions of active compounds in organic solvents are to be further diluted to produce aqueous dispersions, the preferred solvents include acetone and the alcohols. When the liquid carrier is entirely organic in nature, particularly desirable carriers are the petroleum distillates boiling almost entirely under 400* F. at atmospheric pressure and having a flash point above about 80 F. Dispersing and emulsifying agents which may be employed in liquid compositions include condensation products of alkylene oxides with phenols and organic acids, alkyl aryl sulfonates, polyoxyalkylene derivatives of sorbitan esters, complex ether alcohols, mahogany soaps and the like. The surface-active agents are generally employed in the amount of from 1 to percent by weight of the phenolic compound.

Solid compositions containing the active phenolic compound may be prepared by dispersing the compounds in finely divided inert solid carriers such as talc, chalk, gypsum, vermiculite, bentonite and the like, fullers earth, attapulgite and other clays, various solid detergent dispersing agents and solid fertilizer compositions. In preparing such compositions, the carrier is mechani cally ground with the phenol compound or Wet with a solution thereof in a volatile organic solvent. Depending upon the proportions of ingredients, these compositions may be employed without further modification or be considered concentrates and subsequently further diluted with solid surface-active dispersing agent, talc, chalk, gypsum or the like to obtain the desired treating composition. Furthermore, such concentrate compositions may be dispersed in water with or Without added dispersing agent or agents to prepare aqueous soil treating compositions.

Soil treatment compositions may be prepared by dispersing the phenol compounds in fertilizers such as ammonium fertilizer or organic nitrogen fertilizer. The resulting fertilizer composition may be employed as such or may be modified such as by dilution with additional nitrogen fertilizer or with inert solid carrier to obtain a composition containing the desired amount of active agent for treatment of soil. Further, an aqueous dispersion of the phenolic compound fertilizer composition may be prepared and administered to the growth medium. Fertilizer compositions comprising the phenolic compounds in intimate admixture with ammonium fertilizers constitute preferred embodiments of the present invention. In fertilizer compositions comprising a reduced nitrogen fertilizer, it is desirable that the phenolic compound be present in an amount of at least 0.5 percent by weight based on the weight of the nitrogen present in the fertilizer as reduced nitrogen. Thus, when a fertilizer composition contains both reduced nitrogen and other forms of nitrogen such as in the case of ammonium 6 nitrate fertilizer compositions, the amount of the phenolic compound is based on the weight of nitrogen present in the ammonium component.

In operations carried out in accordance with the present invention, the soil may be impregnated in any convenient fashion with the active compounds or a composition containing these agents. For example, these modified or unmodified compositions may be simply mechanically mixed with the soil; applied to the surface of soil and thereafter dragged or disced into the soil to a desired depth; transported into the soil with a liquid carrier such as by injection, spraying or irrigation. When the distribution is carried out by introducing the compounds in the water employed to irrigate the soil, the amount of water is varied in accordance with the moisture content of the soil in order to obtain a distribution of the compounds to the desired depth. The compounds may be readily and conveniently distributed to a depth of from two to four feet by irrigation methods. The preferred methods embrace procedures using any of these steps or combination of steps wherein the compounds are distributed in the soil substantially simultaneously with a reduced nitrogen fertilizer.

The following examples illustrate the invention but are not to be construed as limiting.

EXAMPLE 1 An aqueous ammonium fertilizer composition containing 500 parts by weight of nitrogen and 50 parts by weight of 4-chloro-2-methyl-6-nitrophenol per million parts of aqueous medium was prepared by dispersing a 4 percent (weight by volume of solvent) acetone solution of 4-chloro-2-methyl-6-nitrophenol in aqueous ammonium sulfate solution. (The amount of nitrogen in all examples is based on the nitrogen present in the fertilizer in the reduced form.)

The composition so prepared was employed to treat seed beds prepared from sandy loam soil having a pH of about 8, containing essentially no organic material and having been freed of nitrite and nitrate nitrogen by prior thorough leaching. In the treating operation, the composition Was applied to the seed beds as a soil drench, and the soil in the beds thoroughly mixed to insure a substantially uniform distribution of the composition throughout the soil. The amount of composition employed was sufficient to supply parts by Weight of nitrogen and 10 parts by weight of 4-chloro-2-methyl-6- nitrophenol per million parts by weight of soil. In a check operation, other seed beds prepared of soil also freed of nitrite and nitrate nitrogen, containing substantially no organic material and having a pH of 8 were fertilized with a similar aqueous fertilizer composition containing the same amount of acetone and ammonium sulfate but omitting the phenolic compound. The composition was applied in an amount to supply the same concentration of nitrogen to the soil as the treating composition containing 4-chloro-2-methyl-6-nitrophenol. The soil temperature following distribution remained at about 70 F. for the period of the determination.

At various intervals following treatment, samples of soil were taken from the different seed beds and the extent of nitrification of the added ammonium sulfate fertilizer determined by analyses for nitrate-i-nitrite nitrogen. The determinations were carried out by extracting the nitrate and nitrite from the soil with a saturated calcium sulfate solution, developing color in the clear supernatant of the extract with diphenylamine in sulfuric acid and comparing the color with a standard solution containing known concentrations of nitrate and nitrite ions. This procedure is similar to that described in Colorimetric Methods of Analysis, by F. D. Snell and C. T. Snell, D. Van Norstrand Company, Inc, volume II, 3rd edition, page 801.

The percent nitrification of added ammonium sulfate at various intervals is set forth in the following table:

Experiments were carried out in a manner similar to that described in Example 1 but wherein the final concentrations of the 4-chloro-2-methyl-6-nitrophenol were greatly reduced. Aqueous ammonium fertilizer compositions containing 500 parts by weight of nitrogen and 25 and 10 parts by weight, respectively, of 4-chloro-2-methyl- 6-nitrophenol per million parts of aqueous media were prepared by dispersing a 2 percent (weight by volume of solvent) acetone solution of 4-chloro -2-methy1-6-nitrophenol in aqueous ammonium sulfate solution. The compositions were applied to soil beds in amounts suificient to give concentrations of the 4-chloro-2-methyl-6-nitrophenol therein of 5 parts and 2 parts by weight per million parts by weight of soil, respectively. The degree of nitrification was determined after an interval of 8 days and found to be 0 percent and 15 percent, respectively. Check operations carried out with a composition containing no 4-chloro-2-methyl-6-nitrophenol showed 100 percent nitrification on both determinations.

EXAMPLE 3 Ammonium sulfate and an acetone solution containing 4 percent (weight by volume of solvent) of 4-chloro- 2-nitrophenonl were dispersed in Water to prepare an aqueous composition containing 500 parts by weight of nitrogen and 50 parts by weight of 4-chloro-2-nitrophenol per million parts by weight of ultimate mixture. This composition was applied to seed beds of sandy loam soil similar to that described in Example 1, in an amount sufiicient to provide 100 parts by weight of nitrogen and 10 parts by weight of 4-chloro-2-nitrophenol per million parts by Weight of soil. A check operation was simultaneously carried out on other seed beds employing a similar aqueous fertilizer composition but containing no 4-chloro-2-nitrophenol.

At various intervals following treatment, analyses were made on samples of soil from the different seed beds for their content of nitrite-l-nitrate nitrogen and the percent nitrification of ammonium sulfate determined thereby. The percentage nitrification at various intervals is 8 EXAMPLE 4 An experiment was carried out in a similar manner to that described in Example 3, but wherein the concentra tion of the 4-ch1oro-2-nitrophenol in the aqueous composition was reduced to 25 parts per million. The composition was then applied to soil in an amount sufiicient to give a concentration of the 4-chloro-2-nitrophenol therein of 5 parts by weight per million parts by weight of soil. The degree of nitrification was determined after an interval of 8 days and 15 days and found to be 5 percent and 25 percent, respectively. Check operations carried out with a composition containing no 4-chloro-2- nitrophenol showed percent nitrification on both determinations.

EXAMPLE 5 An aqueous ammonium sulfate composition containing 500 parts by weight of nitrogen and 25 parts by Weight of 2-nitrophenol per million parts by Weight of ultimate mixture was prepared in a manner similar to that described in the preceding examples. This composition was applied to sandy loam soil in an amount sufficient to provide 100 parts by weight of nitrogen and 5 parts by weight of 2-ni-trophenol per million parts by weight of soil. A check operation was carried out simultaneously on other seed beds employing a similar aqueous fertilizer composition but containing no Z-nitrophenol.

At intervals following the treatment, samples of soil from the different seed beds were analyzed for their content of nitrite+nitrate nitrogen and the percent nitrification of ammonium sulfate determined. The results are given in Table III.

Aqueous ammonium sulfate compositions varying in the phenolic component were prepared in a manner similar to that previously described. These compositions containing 500 parts by weight of nitrogen and 50 parts by weight of the respective phenol compounds per million parts by Weight of ultimate mixture were applied to seed beds of sandy loam soil having a pH of about 8, as previously described, in amounts sufiicient to supply 100 parts by weight of nitrogen and 10 parts by weight of the phenol compound per million parts by weight of soil. Check operations were carried out simultaneously on seed beds of similar soil employing an aqueous fertilizer composition in which the phenolic compound was omitted.

At various intervals following treatment, samples of soil from the difierent seed beds were analyzed for their content of nitrite+nitrate nitrogen and the percent nitrification of ammonium sulfate determined. The soil treating composition-s employed and the percentage nitrification at the various observation intervals are set forth in the following Table IV.

9 Table IV Interval Percent Treating composition following nitrifitreatment cation in days Ammonium sulfate+4-chloro-Z-methylphenol 14 Ammonium sulfate (chock) 14 100 Ammonium sulfate+4-cliloro-2-mcthylphenol 21 1O Ammonium sulfate (check) 21 100 Ammonium sulfate+4-bromo 8 13 Ammonium sulfate (check) 8 100 Ammonium sulfate-lt-bromo 15 15 Ammonium sulfate (check) 15 100 EXAMPLE 7 15 Concentrate compositions are prepared as follows:

(A) parts by weight of 4-methyl-2-nitrophenol, 65 parts of xylene and 10 parts of an alkylated aryl polyether alcohol (Triton X-100) are mechanically mixed together to obtain an emulsifiable liquid composition.

(B) 90 parts by weight of 4-bromo-2-nitrophenol and 10 parts of an alkyl aryl sulfonate (Acto 700) are mechanically mixed together to obtain a Water-dispersible mixture.

These compositions may be dispersed in water to produce aqueous compositions having desirable wetting and penetrating properties. These aqueous compositions are then employed to treat soil in an amount suflicient to distribute the phenol compound therein in effective concentrations. The concentrates may also be dispersed in aqua ammonia to prepare fertilizer compositions.

EXAMPLE 8 Fertilizer compositions are prepared as follows:

(A) Sodium, triethylamine and ethanolamine salts of 4-chloro-2-nitrophenol are mechanically mixed in separate portions with diammonium phosphate to prepare reduced nitrogen fertilizer compositions containing 5 percent by weight of a 4-chloro-2-nitrophenol salt.

(B) Ammonium and triethanolamine salts of Z-methyl- 6-nitrophenol are mechanically mixed in separate portions with ammonium nitrate to prepare reduced nitrogen fertilizer compositions containing 3 percent by weight of a 2-methyl-6-nitrophenol salt.

(C) Potassium, calcium and dimethylamine salts of 2-nitrophen0l are mechanically mixed in separate portions with urea to prepare reduced nitrogen fertilizer compositions containing 2. percent by weight of a phenolic salt.

These fertilizer compositions are distributed in soil to nitrogen available for plant growth over a prolonged period of time.

EXAMPLE 9 Aqueous ammonium fertilizer compositions containing 1,000 parts by weight of nitrogen and 50 parts by weight of 4-chloro-2-nitrophenol in a million parts of aqueous media were prepared by dispersing an acetone solution containing 4 percent (Weight by volume of solvent) of 4-chloro-2-nitrophenol in aqueous solutions of various ammonium compounds.

In operations similar to that described in Exarnple 1, the soil in seed beds was treated with the above described compositions to distribute a particular composition throughout the soil in an amount sufficient to supply a concentration of nitrogen in the soil of 200 parts by weight and of 4-chloro-2-nitrophenol of 10 parts by weight per million parts by weight of soil. The treated soil was maintained at 70 F. for the period of the determination. At various intervals, samples of the soil were taken and analyses made to determine the extent of nitrification.

Soils treated with the ammonium phosphates and aqua to ammonia were analyzed for nitrate-I-nitrite nitrogen as previously described. The soils treated with ammonium nitrate were analyzed for residual ammonia by extracting the soil with 2 molar potassium chloride and the amtmonia in the extract determined by comparisons with a standard on a spot plate using 'Nesslers reagent as indioator.

Check operations were simultaneously carried out on other seed beds employing'a similar aqueous fertilizer composition but containing no 4-ohloro-2-n1trophenol. The results of these operations are given in Table V.

Table V Interval Percent Treating composition following nitrifitreatment cation in days Ammonium nitrate+4-chloro-2-nitrophenol 14 0 Ammonium nitrate (check) 14 Ammonium nitrate+4-chloro-2-nitrophenol 27 0 Ammonium nitrate (check) 27 Ammonium nitrate+4-chloro-2-nitrophenoL 70 10 Ammonium nitrate (check) 70 100 Aqua ammonia+4-chloro-2nitrophen 14 15 Aqua ammonia (check) 14 100 Aqua ammonia+4-chloro-2-nitrophenol 27 20 Aqua ammonia (check) 27 100 Diammonium phosphate+4-chloro-2-nitrophenol 14 5 Diammouium phosphate (check) 14 100 Diammonium phosphate+4-chloro-2-nitropheno1 34 5 Diammonium phosphate (check) 34 100 Diammonium phosphate+4-ohloro-2-nitrophcnol 40 10 Diammom'urn phosphate (check) 40 100 Diammonium phosphate+4-ehloro-2-nitrophenol 77 15 Diammonium phosphate (check) 77 100 Monoammonium phosphate+4 chloro 2 nitro phenol 4O 5 Mouoammonium phosphate (check) 40 100 Monoammonium phosphate+4 ehloro 2 nitro phenol 70 1O Mouonmmonium phosphate (check) 70 100 Monoammom'um phosphate+4 ohloro 2 nitro phenol 77 25 Monoammonium phosphate (cheek) 77 100 EXAMPLE 10 A solid fertilizer composition was prepared as follows: (1) an inhibitor component was prepared by (a) mixing and grinding together 0.2 gram of 4-chloro-2-nitrophenol and 0.3 gram of attapulgite, (b) adding 1.5 grams of pyrophyllite thereto and grinding the resulting mixture until a finely powdered uniform composition was obtained; (2) a fertilizer component was prepared by hammermilling together a 50:50 mixture by weight of ammonium sulfate and pyrophyllite to obtain a fine uniform composition; (3) the inhibitor component and fertilizer component were mixed together in various ratios on a roller mill to obtain soil treating compositions containing 4-chloro-2-nitrophenol in varying concentrations expressed in percent based on the nitrogen in the composition. These compositions were employed to fertilize various beds of sandy loam soil containing essentially no organic material and having a pH of about 8. The soil employed had been previously leached to remove all nitrate and nitrite nitrogen constituents. A sutficient amount of water was added to the various beds to give the soil in the beds varying moisture content. The beds were fertilized in areas to be planted by providing depressions and adding thereto the fertilizer treating composition and then covering the composition with soil. The amount of composition employed was sufiicient to supply parts by weight of nitrogen per million parts by weight of soil. The soil was maintained in the temperature range of from 70 to 85 F. for three weeks. At the end of this period, samples of soil were analyzed for content of nitrate-l-nitrite nitrogen to determine the extent of nitrification of the added ammonium sulfate. The results were compared with check determinations wherein no 4-chloro-2-nitrophenol was added to the fertilizer composition. The results obtained are given in Table VI.

Table VI Concentration of 4-chloro-2- Incubanitrophenol as Percent tion pe- Percent percent based moisture riod in nitrificaon the nitrogen in soil days tion in the composition 1 Check.

EXAMPLE 11 Irrigation water was modified by adding an acetone solution containing 5 percent (weight by volume of solvent) of 4-chloro-2-nitrophenol to give a concentration of the phenolic compound therein of 50 parts by weight in a million parts of water.

The water modified as described above was employed to irrigate dry sandy loam soil having a pH of 8 and previously leached to remove any nitrite and nitrate present. The depth of the sandy loam bed was 20-21 inches. An amount of modified water equal to 6 acre inches per acre of soil was added and allowed to equilibrate in the soil by standing for several days. At the end of this period, samples of soil from various depths were taken. To each sample a sufiicient volume of an aqueous ammonium sulfate solution containing 2,500 parts of nitrogen by weight per million parts of water was added to give a composition containing 100 parts by weight of nitrogen per million parts of soil. The fertilized soil samples were thereafter maintained in the temperature range of from 70 to 85 F. At periodic intervals, samples of the soil were taken and analyses made on the ni-trate-l-nitrite nitrogen to determine the extent of nitrification. The results are given in Table Check operations were carried out on the various layers of soil irrigated with unmodified water. It was found in the check operations that after 17 days there was 100 percent nitrification at all depths. of the soil.

EXAMPLE 12 An aqueous soil treating composition containing 100 parts by weight of 4-chloro-2-nitrophenol, 1,000 parts by weight of nitrogen as ammonium sulfate and 500 parts by weight of phosphorus as phosphoric acid was prepared by dispersing a 4 percent (weight per volume of solvent) acetone solution of 4-chloro-2-nitrophenol into an aqueous solution of ammonium sulfate and phosphoric acid.

Pots were prepared for planting with 500 grams of san dy loamsoil having a pH of 8 and a 4 percent moisture content. 200 milliliters of the treating composition prepared as described above was poured over the soil (an amount equal to about 1 inch of liquid) to supply to the soil 4-ohloro-2-ni-trophenol in an amount suificient to give a concentration of 40 parts by weight per million pants 12 by weight of soil and a concentration of nitrogen of 400 parts per million. The treated soil was then covered with paper to reduce evaporation and maintained in the temperature range of from 70 to F.

After a period of six weeks, the soil in the pots was leached with 6 inches of water and thereafter planted with three species. Each pot was planted with four tomato plants, five milo plants and a thick stand of rye. After an appropriate growth interval, the tops of the plants were harvested just above ground level and weighed. The average fresh weight in grams per pot was determined at the time of harvest which was 35 days for tomato plants, 46 days for milo plants and 47 days for rye plants.

A check operation was carried out simultaneously wherein soil in pots was similarly fertilized with a composition containing the same amount of ammonium sulfate,'p hosphoric acid and acetone but no 4-cbloro-2 nitrophenol.

The weights of the plant tops at harvest and the nitrogen content of the soil prior to leaching in both the treating and check operations are set forth in Table VIII.

A solid fertilizer treating composition was prepared by (1) grinding together 1.0 part by weight of 4-chloro- 2-nitrophenol with 1.5 parts by weight of attapulgite, (2) mixing this mixture with 3 times its weight of pyrophyllite, and (3) mixing the resulting mixture with 9 times its weight of a 50/40 mixture of ammonium sulfate and pyrophyllite. This treating composition contained 1 percent by weight of 4-chloro-2-nitrophenol and 50 percent by Weight of ammonium sulfate.

Pots were prepared for planting with 500 grams of sandy loam soil having a pH of 8 and a 4 percent moisture content. 200 milliliters of a phosphoric acid solution containing 500 parts by weight of phosphorus per million parts of media was poured over soil. The soil was then allowed to dry. Thereafter, a hole about %-1 inch deep was made in the center of each pot, and 2 grams of the solid fertilizer treating composition prepared as described above placed therein. The holes were closed by compressing the soil together. "The soil thus treated contained 40 parts by weight of 4-chloro-2-nitrophenol and 400 parts by weight of nitrogen per million parts by weight of soil. The pots were then covered with paper to reduce evaporation and maintained in the temperature range of from 70 to 80 F. for five weeks. At the end of this period, the soil in the pots was leached with 6 inches of water and then planted with 4 tomato plants per pot. After a growing period of 48 days, the tops of the plants were harvested by cutting them off at the ground level and the average fresh weight in grams per pot determined.

A check operation was carried out simultaneously wherein the soil in the pots was similarly treated with fertilizer composition containing no 4-ohloro-2-nit.rophenol.

The average weight of the plant tops at harvest in both the treating and check operations are set forth in Table IX.

I claim:

1. A method for suppressing the nitrification of ammonium nitrogen present in soil and preventing rapid loss of ammonium nitrogen therefrom which comprises impregnating soil below the soil surface in the growing area thereof in concentration sufficient to suppress nitrification, with a phenol compound, said phenol compound being selected from the group consisting of (l) phenols having the formula wherein X represents a member of the group consisting of hydrogen, methyl, chlorine and bromine, Y represents a member of the group consisting of hydrogen and nitro, and Z represents a member of the group consisting of hydrogen and methyl; and wherein the phenolic ring is substituted by at least one of (a) a nitro radical and (b) both a methyl and a halo radical; and wherein the phenolic ring contains no more than one methyl radical; and (2) salts of said phenols, said concentration being from about 2 to 150 parts by weight per million parts by weight of soil.

2. A method according to claim 1 wherein the phenol compound is 4-ohloro-2-nitrophenol.

3. A method according to claim 1 wherein the phenol compound is 2-nitrophenol.

4. A method according to claim 1 wherein the phenol compound is 2-methyl-4-chlorophenol.

5. A method according to claim 1 wherein the phenol compound is 2-met-hyl-4-bromopheno1.

6. A method according to claim 1 wherein the phenol compound is 2-methyl-4-chloro-6-nitrophenol.

7. A method acccording to claim 1 wherein the phenol compound is added in an amount sufficient to give a concentration in the soil of from 2 to 50 parts by weight per million parts by weight of soil.

8. A method according to claim 7 wherein the phenol compound is introduced in the soil at a point near the roots of the growing plants.

9. A method for treating soil to inhibit the conversion therein of ammonium nitrogen to nitrate and nitrite nitrogen and to prevent rapid loss of ammonium nitrogen therefrom which comprises impregnating the soil below the soil surface in the growing area thereof in an amount sufiicient to inhibit nitrification with a composition comprising a phenol compound in intimate admixture with a soil treatng adjuvant, the phenol compound being selected from the group consisting of (1) phenols having the structure and and (2) salts of these phenols; and wherein in the above formulae, A represents a member of the group consisting of hydrogen, bromine, chlorine and methyl, B represents a member of the group consisting of hydrogen, bromine and chlorine, and C represents a member of the group consisting of bromine and chlorine, said impregnation being so carried out as to provide a concentration in soil of :at least 2 parts by weight of the phenol compound per million parts by weight of soil.

10. A method according to claim 9 wherein the adjuvant is a reduced nitrogen fertilizer composition, wherein said reduced nitrogen fertilizer is a fertilizer selected from the group consisting of ammonia, ammonium salts and urea.

11. A fertilizer composition comprising a major amount of a reduced nitrogen fertilizer as source of ammonium ions and a phenol compound selected from the group consisting of (1) phenols having the formula wherein X represents a member of the group consisting of hydrogen, methyl, chlorine and bromine, Y represents a member of the group consisting of hydrogen and nitro, and Z represents a member of the group consisting of hydrogen and methyl; and wherein the phenolic ring is substituted by at least one of (a) a nitro radical and (1)) both a methyl and a halo radical; and wherein the phenolic ring contains no more than one methyl radical; and 2) salts of said phenols; and wherein the phenol compound is present in a concentration of at least 0.5 percent by weight based on the weight of the reduced nitrogen present in the fertilizer; and wherein said reduced nitrogen fertilizer is selected from the group consisting of ammonia, ammonium salts and urea.

12. A fertilizer composition comprising a major amount of a reduced nitrogen fertilizer as source of ammonium ions and 4-chloro-2nit-rophenol as the phenol compound wherein said phenol compound is present in a concentration of at least 0.5 percent by weight based on the weight of the reduced nitrogen present in the fertilizer; and wherein said reduced nitrogen fertilizer is a fertilizer selected from the group consisting of ammonia, ammonium salts and urea.

References Cited in the file of this patent UNITED STATES PATENTS 1,983,546 Johnson Dec. 11, 1934 2,188,734 Carswell Jan. 30, 1940 2,312,801 Craig et al. Mar. 2, 1943 2,314,091 Jones Mar. 16, 1943 2,344,063 Schotte et al. Mar. 14, 1944 2,599,827 Hansberry June 10, 1952 

1. A METHOD FOR SUPPRESSING THE NITRIFICATION OF AMMONIUM NITROGEN PRESENT IN SOIL AND PREVENTING RAPID LOSS OF AMMONIUM NITROGEN THEREFROM WHICH COMPRISES IMPREGNATING SOIL BELOW THE SOIL SURFACE IN THE GROWING AREA THEREOF IN CONCENTRATION SUFFICIENT TO SUPPRESS NITRIFICATION, WITH A PHENOL COMPOUD, SAID PHENOL COMPOUND BEING SELECTED FROM THE GROUP CONSISTING OF (1) PHENOLS HAVING THE FORMULA 